Process and apparatus for the production of methanol from condensed carbonaceous material

ABSTRACT

An intergrated recycle process for the production of methanol from a process synthesis gas produced by hydrogasification of a condensed carbonaceous feedstock to produce a process gas which is reacted in a steam pyrolysis reactor with additional natural gas and steam to produce said synthesis gas containing hydrogen and carbon monoxide in more than a 2:1 molar ratio which constituents in turn are reacted in a methanol synthesis reactor to produce methanol. The important factor in this process includes the sequence of reactors of the condensed carbonaceous material: a hydrogasification reactor; the stream and natural gas pyrolysis reactor; the methanol synthesis reactor and the recycling to the hydrogasification reactor of the hydrogen-rich gas stream remaining after the methanol synthesis and separation of the methanol product.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is related to a method and apparatus for theproduction of methanol and more specifically to a continuous method andapparatus using condensed carbonaceous raw materials such as coal,natural gas, (i.e.; methane) wood, municipal solid waste, other biomassand other carbonaceous material for such production.

2. Description of the Prior Art

Methanol, which was first discovered in the late 1600's, has found usesas a chemical feedstock, as well as an efficient fuel. Its earliest andlargest use to date is as a feedstock in the production of formaldehyde.While in recent years such use has decreased, methanol has foundincreasing use in the production of such materials as acetic acid andmethyl tert-butyl ether (MTBE-a gasoline additive). In addition,methanol is being used directly (with increasing demand) as a fuel inrace cars, in farm equipment and, in some areas, as a general purposeautomotive fuel.

As will be discussed further below, there are several commerciallyviable methods of producing methanol. While different feedstocks areused and various processing steps are involved in these methods, theyall must produce or otherwise provide carbon monoxide and hydrogen in amolar ratio of 1 mole of CO to 2 moles of H₂. These reactants are thenreacted in a methanol synthesis reactor to produce methanol inaccordance with the following exothermic reaction:

    CO+2H.sub.2 →CH.sub.3 OH

The processes known in the art often also produce carbon dioxide which,if fed into the methanol synthesis reactor, results in a lower methanolyielding reaction which competes with the above reaction for thevaluable hydrogen as follows:

    CO.sub.2 +3H.sub.2 →CH.sub.3 OH+H.sub.2 O

The oldest method of producing methanol on a commercially significantscale was the destruction distillation of wood. However, this method isno longer practiced in the United States.

A current conventional source of methanol, which produces approximatelyninety (90%) percent of the methanol used, is the conversion of naturalgas to methanol. This process involves the catalyzed conversion orreforming of the natural gas with steam to a synthesis gas containingprincipally carbon monoxide and hydrogen which synthesis gas issubsequently convened to methanol in the presence of a second catalyst.Excess hydrogen is either vented or used as a fuel.

A second method of preparing methanol taught in the art uses condensedcarbonaceous material such as fossil fuels, biomass, wood, paper,plastic and the like. This approach involves gasifying the condensedcarbonaceous material with steam and oxygen at elevated pressure andtemperature to produce hydrogen and carbon monoxide in approximately a1:1 molar ratio. As discussed above, a 2:1 molar ratio of hydrogen tocarbon monoxide is necessary for the production of methanol. In thisprocess, that is accomplished by further reacting some of the carbonmonoxide with steam to form the additional hydrogen required to producemethanol. This second step takes place in a shift reactor and alsoproduces carbon dioxide. The gas from the shift reactor must be solventwashed or scrubbed to separate and remove the carbon dioxide, which isvented to the atmosphere, leaving a process gas containing mainlyhydrogen and carbon monoxide in a molar ratio of approximately 2 to 1for feeding to a catalytic methanol convertor, where methanol isproduced. Excess gas is either used as fuel or is vented,

While this approach may use a broader class of feed material than theforst process described, it does not achieve high methanol yields perquantity of feedstock and has than desirable thermal and carboncondensed efficiency. Furthermore, the second method requires the shiftreaction (an extra step) to produce H₂ /CO in the 2:1 molar ratio asneeded by the methanol synthesis reactor to maximize the production ofmethanol per unit of feedstock. In addition, this second process alsoproduces carbon dioxide in large quantities which must be removed priorto entry of the shift reaction products into the methanol synthesisreactor to prevent reduction of the methanol yield. Furthermore, thisprocess also requires pure oxygen for the gasifications reaction whichis endothermic.

A more detailed discussion of the above processes can be found inKirk-Othmer Encyclopedia of Chemical Technology, Vol. 15, pp 398-415,John Wiley & Sons (1978).

It is therefore an object of the present invention to provide anefficient method and apparatus for the production of methanol fromcondensed carbonaceous material.

It is another object of the present invention to provide a method andapparatus for the production of methanol which produces a higher yieldof methanol per unit feedstock.

It is another object of the present invention to provide a method andapparatus for the production of methanol with a reduced mass and thermalloss.

It is still another object of the present invention to provide a methodand apparatus for the production of methanol which does not require ashift reactor to produce hydrogen and carbon monoxide in a molar ratioof 2:1.

It is yet another object of the present invention to provide a methodand apparatus for the production of methanol having reduced carbondioxide emissions and which eliminates the need for carbon dioxideremoval.

It is still another object of the present invention to provide a methodand apparatus for the production of methanol which eliminates the needfor oxygen.

It is yet another object of the present invention to provide a methodand apparatus for the production of methanol which gives a higher yieldof methanol per unit of feedstock and has a higher thermal and carbonconversion effeciency than the conventional processes.

The above and other objects and advantages of the present invention willbecome apparent from the following specification read in conjunctionwith the annexed drawings.

SUMMARY OF THE INVENTION

This invention relates to the production of methanol by conversion ofcondensed carbonaceous raw material and the apparatus for same. Theprocess of the present invention is comprised of three steps, the firstof which is the hydrogasification of solid and/or liquid carbonaceousmaterials with hydrogen gas under elevated pressure and temperature toconvert the carbonaceous material to a process gas rich in methane andwith a low carbon dioxide content. The hydrogasification step is eitherexothermic or at least thermally neutral and therefore requires noadditional input of thermal energy.

The methane-rich process gas from the first step of the process thenundergoes steam pyrolysis which is accomplished with the addition ofmore methane to form a synthesis gas containing higher amounts of carbonmonoxide and which is rich in hydrogen. This pyrolysis step takes placein the presence of a catalyst at a higher temperature and either at thesame or lower pressure than the hydrogasification step. The steampyrolysis step is endothermic and requires additional thermal energyinput.

Finally, the hydrogen rich and carbon monoxide containing synthesis gasproduced in step two is combined by a catalytic reaction in a methanolsynthesis reactor at a lower temperature and the same pressure as stepone to form methanol. The methanol may then be separated from theproduct gas stream produced in the methanol synthesis reactor by knownfractionating techniques.

An important feature of the present invention is that the hydrogen usedin the first step of the process is provided by recycling the productgas stream from the methanol synthesis reactor left after the separationof the methanol. The recycle stream is rich in hydrogen and alsocontains unused methane. The use of this recycled stream enhances andimproves the yield of the hydrogasification step described above andconserves the mass and energy balance of the entire system and thusprovides for higher mass and thermal efficiency of the entire process.

The process and apparatus of the present invention may successfully useas a feedstock all condensed carbonaceous materials including fossilfuels such as oil, coal or natural gas; agricultural products such ascorn, rice and the like; wood; plant matter; marine plant matter such asseaweed, kelp, marine organisms; waste material such as householdgarbage, paper, municiple solid waste and the like.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a simplified schematic process flow chart of the process ofthis invention;

FIG. 2 shows computer simulated results of the process of the presentinvention with biomass and natural gas as feedstock; and

FIG. 3 shows another computer simulated result of the process of thepresent invention with coal and natural gas as the feedstock.

DETAILED DESCRIPTION OF THE INVENTION

Referring to FIG. 1, an embodiment of the overall process is shown whichmay be divided into three principal sections: Hydrogasification, Steampyrolysis and Methanol synthesis.

As shown, a solid or liquid carbonaceous material and steam are fed intothe hydrogasification reactor 2 along with a recycled hydrogen rich gas.These components are reacted to produce a process gas rich in methaneand containing minor amounts of carbon dioxide, and other impurities.The main hydrogasification reactions are exothermic and the entirehydrogasification step, if not exothermic, is at least thermallyneutral, Therefore, requires no additional input of energy, In addition,carbon dioxide production is minimized by this approach and therefore nocarbon dioxide removal step is required.

This above-described process takes place in a hydrogasification reactor2 which may be any solid-gas contact reactor but preferably a fluidizedbed reactor with particles of the carbonaceous feedstock flowingdownward due to gravity balanced by the upward flow of process gas whichfluidizes the solid carbonaceous particles. In accordance with thepresent invention the hydrogasification reactor 2 is operated at atemperature ranging from 700° C. to 900° C. and a pressure which canrange from 10 atmospheres to 100 atmospheres. The preferred combinationof this temperature and pressure is 800° C. to 900° C. and 30 to 50atmospheres which combination maximizes the concentration of methane inthe process gas produced by this hydrogasification step.

As will be clear to one skilled in the art, the carbonaceous materialused in the process of the present invention is one of the sources ofthe carbon which will eventually be incorporated in the methanolproduced by this process. Ideally, the material used will containbetween 30% and 80% by weight carbon, the balance being comprised ofbonded hydrogen, oxygen and containing water, ash, sulfur, nitrogen andother impurities. Additional elemental carbon, hydrogen and oxygen, asneeded, are provided to the hydrogasification reactor 2 by the recycledhydrogen rich steams described below and the additional steam.

In general, the reactions that take place in the hydrogasificationreactor 2 and the stoichiometric requirements of such reactions areexpressed by the following general equations:

    (1) C+2H.sub.2 →CH.sub.4                            (1)

    (2) C+H.sub.2 O→CO+H.sub.2                          (2)

    (3) 2H.sub.2 O+C→CO.sub.2 +2H.sub.2                 (3)

    (4) CO.sub.2 +H.sub.2 →CO+H.sub.2 O                 (4)

Reactions (1) and (2) are the main reaction occuring in theHydrogasification reactor 2 with reactions (3) and (4) occuring to alesser extent. Reaction (4) not only consumes the carbon dioxideproduced in reaction (3) but also any carbon dioxide contained in thehydrogen rich recycle stream discussed below. The final composition ofthe process gas from the hydrogasification reactor is determined by thethermodynamic equilibrium and kenetics among the five (5) gaseouscomponents of said process gas: hydrogen, methane, carbon monoxide,carbon dioxide and water.

The hydrogasification reactions, in addition to producing theabove-described products will also (depending on the specific feed stockemployed) produce a variety of minor gaseous by-products, such as H₂ S,as well as some char and ash. The char and ash is removed from thereactor and disposed of properly. The gaseous products remain in theprocess gas produced by this step, are passed to the next step andcontribute to maintaining the overall mass balance of this process.

The carbonaceous feedstock will sometimes contain impurities that willdetrimentally impact the catalysts or reactions employed in the presentprocess. If such is the case, additional components may be employed inthe hydrogasification reactor 2 to eliminate these impurities. Forexample, if any sulfur containing coal is employed in the feedstock thesulfur, which may "poison" the catalysts used in subsequent steps, mustbe removed. This is typically accomplished by the addition of limestoneto the hydrogasification reactor 2 which reacts with the sulfur toproduce a product easily removed along with the char and ash.

The overall hydrogasification process is either exothermic or, at least,thermally neutral. Therefore, no additional thermal energy is needed inthis reactor. As a result of the exothermic nature of the overallreactions, no oxygen (which is typically required in a conventionalgasification reactor since the reaction is endothermic and thus thermalenergy is needed) is required. Furthermore, the carbon dioxideproduction in the hydrogasification reactor 2 is minimized. Depending onthe carbonaceous feedstock used, the process gas produced by thehydrogasification reactor 2 usually contains five (5) significantgaseous components: hydrogen, methane, carbon monoxide, carbon dioxideand steam; approaching equilibrium amounts, the major gas componentbeing methane which can vary in the range 20% to 50% by volume.

As described above, the process of the present invention is a continuousprocess. In the hydrogasification reactor 2, the residence time of thesolid phase (i.e. the time a particle of carbon in the condensedcarbonaceous feedstock remains in a solid phase in the reactor) canrange from five (5) minutes for biomass to one (1) hour for coal, thepreferred residence time being in the range of 10 to 30 minutes.

As will be clear to one skilled in the art, the purpose behind thereaction in the hydrogasification reactor 2 is to produce methane andalso to begin to form carbon monoxide which is required in a subsequentstep of the process of the present invention. While this goal may beachieved without the introduction of steam into the hydrogasificationreactor 2 [see reaction equation (1) above], the presence of the steamproduces additional carbon monoxide [see reaction equation (2) above]and aids in the maximum conversion of carbon in the feedstock.

The hydrogasification reactor process gas is next passed through anexpander 8 which reduces the pressure and temperature of the process gaswhich is then fed into a steam pyrolysis reactor 4 for the next step ofthe process. This next step takes place in a steam pyrolysis reactor 4which has similarities to a conventional steam reformer of natural gas.

The steam pyrolysis reactor 4 is comprised of a tubular heat exchangerset into a heated gas furnace. The gas furnace is at low atmosphericpressure. The process gas flows inside the heat exchanger tubes and isheated by the heat transfer through the tube walls by the hot furnacegases. As further described below, this step requires a catalyst whichis packed inside the heat exchanger tubes so that as the process gaspasses through the steam pyrolysis reactor 4 it passes through and incontact with the catalyst.

The steam pyrolysis reactor 4 may operate in the range of 800° C. to1200° C. and at a pressure in the range of 10-100 atmosphere with 1000°C. and 30 atmospheres being the preferred operating conditions. Theresidence time of the process gas within the reactor is relatively shortand depends on the heat flux in the reactor tubes, the residence time ofless than 10 seconds being typical to establish equilibrium of thereaction gases in the steam pyroysis reactor 4.

As indicated above, the methane rich process gas stream from thehydrogasification reactor 2 is fed into the steam pyrolysis reactor 4and while there is steam and a significant amount of methane containedin this process gas, additional steam and methane is provided to thesteam pyrolysis reactor 4 from an external source to provide forestablishing equilibrium conditions of the reactants in the steampyrolysis reactor 4. The major reaction that takes place in the steampyrolysis reactor 4 is described as follows:

    (5) H.sub.2 0+CH.sub.4 →CO+3H.sub.2                 (5)

As described above, the steam used in this reaction is provided by thesteam content of the process gas from the hydrogasification step and thesteam addition from an external source. While there are other sidereactions and products passing through the steam pyrolysis reactor 4,the main and desired products of the reactor 4 is a synthesis gascontaining carbon monoxide and which is rich in hydrogen.

The composition of the synthesis gas produced by the the steam pyrolysisreactor 4 is controlled by the approach to thermodynamic equilibrium ofthe gaseous components: hydrogen, carbon monoxide, carbon dioxide,methane and steam at the pressure and temperature conditions of reactor4. The ratio of hydrogen and carbon monoxide (the major constituents ofthe synthesis gas stream) is greater than a 2 to 1 molar ratio and canrange from 2.5 to 1 up to 6.5 to 1 and in a preferred molar ratio ofbetween 2.5 and 4.5. The carbon monoxide and hydrogen typically formapproximately 80% or more of the the volume of the synthesis gas streamproduced by pyrolysis reactor 4.

The steam pyrolysis reaction is endothermic and requires thermal energyinput which as discussed above is provided by a gas fired furnance. Thecombustion gases typically employed to provide the thermal energy is amixture of natural gas (methane), purge gas and air.

The above-described steam pyrolysis reaction is usually performed in thepresence of a catalyst in order to improve the rate of reaction toapproach thermodynamic equilibrium values for the reactions seen in thereactor. Suitable catalysts include any of the metal oxide classcatalyst and preferably include nickel oxide based catalysts.

In the third step of this process, the carbon monoxide and hydrogencontaining synthesis gas produced in step two are reacted in a methanolsynthesis reactor 6 operated at approximately 50 atmospheres and 260° C.by a catalyzed reaction to produce methanol in accordance with thefollowing major reaction (6) and minor (due to low CO₂ content of thesynthesis gas) reaction (7):

    (6) CO+2H.sub.2 →CH.sub.3 OH                        (6)

    (7) CO.sub.2 +3H.sub.2 →CH.sub.3 OH+H.sub.2 O       (7)

A suitable catalyst for this reaction is any one which will facilitatethe above reaction at a suitable rate at the above recited reactiontemperature and pressure, while reducing any side reactions that wouldreduce the methanol production. The most often used catalyst in theprocess is the well known Cu/Zn based catalyst (ICI low pressurecatalyst).

The gaseous output of the methanol synthesis reactor, in addition tocontaining methanol, contains significant quantities of other gaseouscomponents such as water, unreacted carbon monoxide, carbon dioxide,methane, and the like, and is rich in hydrogen. However, since theboiling point of the methanol (and water) is significantly higher thanthe other components the methanol and water are easily separated fromthe output gases and are further separated from each other, bytechniques known in the art such as condensation and fractionation, toproduce concentrated methanol.

As indicated above, the product gas stream remaining after the removalof methanol is rich in unreacted hydrogen. Furthermore, as describedrelative to the hydrogasification reaction, hydrogen is an important andnecessary reactant introduced to the hydrogasification reactor 2 forreaction with the carbonaceous feedstock. Since hydrogen is availablefrom the product stream from the methanol sythesis reactor 6, inaccordance with the present invention this hydrogen rich product streammay be recycled to the hydrogasification reactor 2 so that no externalsource of hydrogen is neccessary. In addition, the other component ofthe recycled product stream help maintain the overall mass balance ofthe process.

It will be clear to one skilled in the art and as depicted in FIG. 1, acertain amount of the recycled stream must be vented from the process topurge the system of inert gases such as nitrogen which may build up anddilute the process gases. This is referred to as purge gas.

The process gas stream emerging from the steam pyrolysis reactor 4 musthave a substantial reduction in temperature prior to its being fed intothe methanol synthesis reactor 6. While this heat may be discharged tooutside cooling water or the atmosphere, in accordance with the presentinvention this gas stream may be fed to the high temperature side of aheat exchanger 14 with the recycled gas discussed above being fed to thelow temperature side of said heat exchanger 14 which will partiallyreduce the temperature of the steam pyrolysis reactor gas stream andalso increase the temperature of the recycled stream to the operatingtemperature of the hydrogasification reactor. This partially temperaturereduced gas stream may then be fed through another heat exchanger 12 tofurther reduce the temperature of the process gas feed fed into themethanol synthesis reactor 6. The heat extracted by the heat exchanger12 can be used to produce steam which can be used as a feed to thehydrogasification reactor 2 and the steam pryolysis reactor 4, or forgeneration of power in a steam driven turbogenerator.

If required, a compressor unit 10 is provided after the beat exchanger12 to raise the pressure of the process gas to the pressure required bythe methanol synthesis reactor 6.

The process of the present invention is illustrated by computer processsimulations, the results of which are shown in FIGS. 2 & 3. Thesesimulations were run assuming standard thermodynamic equilibrium datafor the five gaseous constituents seen in the present process: hydrogen,methane, carbon monoxde, carbon dioxide and water and in equilibriumwith condensed carbon species in the hydrogasification reactor 2. Inaddition to these computer simulations of the process of the presentinvention, actual tests were performed in the laboratory to verify thesimulation results and to obtain rate data.

The process of the present invention is exemplified by the followingexamples generated by the above-discussed simulation. In interpretingthe results of these examples the following definitions are given:##EQU1##

It should also be noted that, since the present process is continuous,the data given in the following examples is on a unit feedstock and unitrate basis; i.e.; 100 kg wood per unit time or 100 kg coal per unittime.

EXAMPLE 1

Using the apparatus described above and shown in FIG. 1, the process ofthe present invention was simulated using wood as the carbonaceousfeedstock. Referring to FIG. 2, it can be seen that the feedstock fedinto the hydrogasification reactor is 100 kg wood with 10 kg. steam and12.14 kmol of a recycle stream containing 21.48% by volume methane and68.92% by volume hydrogen gas and is operated at the conditions asspecified in FIG. 2 at 800° C. temperature and 50 atmospheres. The steampyrolysis reactor is operated at 30 atmospheres and 1000° C. and themethanol synthesis reactor is operated at 50 atmospheres and 260° C.

With the feedstocks and conditions indicated in FIG. 2, 201.1 kg ofmethanol are produced. The embodiment, as shown in FIG. 2, has an HGRcarbon conversion of 84% and overall carbon conversion efficiency of69.8%, a thermal efficiency of 71.3% and a carbon dioxide emission of103 lbs CO₂ /MMBTU of methanol.

EXAMPLE II

Referring to FIG. 3, it can be seen that the feedstock fed into thehydrogasification reactor is 100 kg coal, 10 kg of steam and 19.24 kmolof a recycle stream containing 12.8% by volume methane and 76.52% byvolume hydrogen gas and is operated at the conditions as specified inFIG. 3 at 900° C. temperature and 50 atmospheres pressure. The steampyrolysis reactor is operated at 30 atmospheres and 1000° C. and themethanol synthesis reactor at 50 atmospheres and 260° C. Additives suchas limestone are added to the hydrogasification reactor to removecontaminants such as sulfur which would affect catalysts used in theprocess.

With the feedstocks and conditions indicated in FIG. 3, 225.2 kg of themethanol is produced. The embodiment as shown in FIG. 3 has an HGRcarbon conversion efficiency of 68% and an overall carbon conversion of62.8%, a thermal efficiency of 64.6% and a carbon dioxide emission of192 lbs CO₂ /MMBTU of the methanol thermal energy.

As will be clear to those skilled in the art, the present inventionrelates to using both condensed carbonaceous materials and methane toproduce methanol. Suprisingly, this combined process produces moremethanol than that which would be produced from each of the conventionalprocesses operating separately on each of the above feedstocks. Thisfact is demonstrated by the results shown in attached tables.

TABLE 1 gives typical examples of process parameters successfully usedin accordance with the present invention for both biomass/methane andcoal/methane feedstocks. TABLES 2 and 3 compare the processes of thepresent invention with the above described conventional process in twoways: (1) when the conventional plant handles each feedstock alone and(2) when both feedstocks are fed together into a single conventionalsteam-oxygen gasification plant or steam gasification plant.

By comprising the results detailed in TABLES 1, 2 & 3, it can be seenthat the three step recycling process of the present invention producesfrom at least 15% to 40% higher yields of methanol per unit of naturalgas and per unit of biomass feedstock than the optimum conventionalsteam reforming or gasification process for each of the feedstock aloneor in a combined conventional steam reforming process. Also the carbondioxide emission from this new process is from about 15% to as high as50% less than CO₂ emission from the conventional plants.

Table 2 indicates that a biomass/natural gas process operated inaccordance with the present invention produces over three (3) times moremethanol per unit of biomass and 1.5 times more methanol per unit ofmethane than each of the best conventional plants, 15.3% more methanolthan two (2) conventional plants each operating on the same quantity offeedstock. Furthermore, the carbon dioxide emmision is 22.7% less forthis process than for the conventional.

Table 3 shows that for a coal and natural gas process operated inaccordance with the present invention, the methanol yield per unit ofcoal is over 4 times greater than the yield of a conventional coalconversion plant and 1.6 times per unit of natural gas than that of aconventional plant, and this process produces 18.1% greater yield thantwo separate conventional plants.

The process of the present invention has the following beneficialfeatures for production of methanol from condensed carbonaceousmaterials compared to the conventional processes:

1. There is no oxygen plant.

2. There is no shift reactor.

3. The hydrogasification reactor can be designed to be energy neutralsince the basic hydrogasification reaction of hydrogen with condensedcarbonaceous material is exothermic.

4. The two consecutive steps of hydrogasification followed by steampyrolysis in accordance with the present invention yields a highercarbon monoxide yield than the conventional process from which methanolis produced.

5. The process of the present invention is totally intergrated whichmakes maximum use of the mass of the feedstock, minimizes heat losses,and maximizing energy utilization.

                  TABLE 1                                                         ______________________________________                                        FEEDSTOCK      BIOMASS/CH.sub.4                                                                           COAL/CH.sub.4                                     ______________________________________                                        Pressure                                                                      HGR (atm)      50           50                                                SPR (atm       30           30                                                Temp                                                                          HGR (C)        800          900                                               SPR (C)        1000         1000                                              MSR (C)        260          260                                               Dry feedstock (kg)                                                                           88.2         91.4                                              moisture (kg)  11.8         9.6                                               CH.sub.4 to SPR (kg)                                                                         50.0         50.0                                              as fuel (kg)   33.1         40.1                                              total (kg)     83.1         90.1                                              Steam to HGR (kg)                                                                            10           10                                                to SPR (kg)    90           160                                               total (kg)     100          170                                               Steam Maked (kg)                                                                             149          191                                               HGR Converse (%)                                                                             84.1         68.3                                              MeOH (kg)      201.1        225.2                                             MeOH/Wood (kg/kg)                                                                            2.28                                                           MeOH/Coal (kg/kg)           2.46                                              MeOH/CH.sub.4 (kg/kg)                                                                        2.42         2.50                                              MeOH/Feed (kg/kg)                                                                            1.17         1.24                                              G/MeOH (kmol/kg)                                                                             0.07         0.09                                              Carbon eff. (%)                                                                              69.8         62.8                                              Thermal eff. (%)                                                                             71.3         64.6                                              CO.sub.2 (lb/MMBTU)                                                                          102          192                                               Gas temp. to HGR (c)                                                                         836          770                                               ______________________________________                                         HGR-Hydrogasification Reactor                                                 SPRSteam Pyrolysis Reactor                                                    MSRMethanol Synthesis Reactor                                            

                  TABLE 2                                                         ______________________________________                                                      Conventional Process                                                                                     BM/                                              Present                BM/   NG**                                             Inven-  BM      NG     NG    Gast/                                Factor      tion    Gasifi. Reform.                                                                              Gasf. Refm.                                ______________________________________                                        Foodstock                                                                     DAF Wood, kg                                                                              88.2    88.2           88.2  88.2                                 CH4, kg     83.1    --      83.1   83.0  83.7                                 O2, kg      --      44.1    --     100.0 --                                   Thermal Eff., %                                                                           71.3    52.4    64.0   51.0  61.0                                 Carbon Conv., %                                                                           69.8    38.0    78.0   49.9  59.8                                 Methanol yield                                                                kg MeOH/kg Wood                                                                           2.28    0.51    --     1.63  1.96                                 kg MeOH/kg CH4                                                                            2.42    --      1.56   1.73  2.07                                 kg MeOH/kg total                                                                          1.17    --      --     0.79  1.01                                 MeOH Product, kg                                                                          201     44.8    129.6  143.8 173.0                                Total, kg   201     174.4        143.8 173.0                                  % increased MeOH                                                                          --      15+            38    16                                   by Hynol over                                                                 conv. processes                                                               CO.sub.2 emmision,                                                                        103     132            150   121                                  lb/MMBTU                                                                      % reduced CO.sub.2 by                                                                             22+            150   121                                  Hynol compared to                                                             conv. processes                                                               ______________________________________                                         *Wood and natural gas are gasified with oxygen at 1000° C. The exi     gas of the gasifier then goes through the shift reactor and the methanol      synthesis reactor. The off gas is used as fuel for oxygen plant.              **Wood and natural gas are gasified with steam at 800° C. The exit     gas of the gasifier than goes through the steam reforming reactor             (1000° C.) and the methanol synthesis reactor. The off gas is used     as one of the fuels for both gasification and steam reforming.                + Process of the present invention produces (201.1 - 174.4) ×           100/174.4 = 15.3% more methanol than two separate conventional processed      do.                                                                           ++ Process of the present invention (132 - 103) × 100/132 = 22% of      CO.sub.2 emission, compared with two separate conventional processes.    

                  TABLE 3                                                         ______________________________________                                                    Conventional Process                                                        Present                Coal/ Coal/NG**                                        Inven-  Coal    NG     NG    Gasf./                                 Factor    tion    Gasifi. Reform.                                                                              Gasf. Refm.                                  ______________________________________                                        Feedstock                                                                     DAF Coal, kg                                                                            91.4    91.4           91.4  91.4                                   CH4, kg   90.1,   --      89.0   90.0  89.1                                   O2, kg    --      73.1    --     120.0 --                                     Thermal Eff.,                                                                           64.6    50.8    64.0   46.9  53.6                                   Carbon Conv.,                                                                           62.8    25.1    78.0   45.6  52.0                                   %                                                                             Methanol yield                                                                kg MeOH/kg                                                                              2.46    0.57    --     1.79  2.03                                   Coal                                                                          kg MeOH/kg                                                                              2.50    --      1.56   1.81  2.08                                   CH4                                                                           kg MeOH/kg                                                                              1.24    --      --     0.86  1.03                                   total                                                                         MeOH Product,                                                                           225     51.9    138.8  163.3 185.7                                  kg                                                                            Total, kg 225     190.7        163.3 185.7                                    % increase                                                                              --      18+            38    21                                     MeOH by                                                                       Hynol over                                                                    conv. processes                                                               CO2 emmision,                                                                           190     362            264   229                                    lb/MMBTU                                                                      % reduced CO2     48++           28    17                                     by Hynol                                                                      compared to                                                                   conv. processes                                                               ______________________________________                                         *Coal and natural gas are gasified with oxygen at 1000° C. The exi     of gas of the gasifier then goes through the shift reactor and the            methanol synthesis reactor. The off gas is used as fuel for oxygen plant.     **Coal and natural gas are gasified with steam at 900° C. the exit     gas of the gasifier then goes through the steam reforming reactor             (1000° C.) and the methanol synthesis reactor. The off gas is used     as one of the fuels for both gasification and steam reforming.                + Process of the present invention produces (225.2 - 190.7) ×           100/190.7 = 18.1% more methanol two separate conventional processes do.       ++ Process of the present invention reduces (362 - 190) × 100/362)      47.5% of CO2 emmision, compared with two separate conventional processes.     NG Natural Gas                                                           

What is claimed is:
 1. An intergrated recycle process for the productionof methanol from a condensed carbonaceous feedstock selected from thegroup consisting of coal, biomass, wood, agricultural products andmunicipal solid wastes comprising:a) hydrogasifying said feedstock in ahydrogasification reactor with a recycled hydrogen rich gas stream toproduce a process gas stream rich in methane; b) steam pyrolyzing saidprocess gas stream in a second stage steam pyrolysis reactor in thepresence of a catalyst to produce a synthesis gas containing mainlycarbon monoxide and hydrogen with small amounts of carbon dioxide; c)reacting said carbon monoxide and hydrogen synthesis gas in a thirdstage methanol synthesis reactor in the presence of a catalyst to form aproduct gas stream containing methanol; d) removing said methanol fromsaid product gas stream leaving product gas stream rich in hydrogen; ande) recycling said hydrogen rich product gas stream to supply thehydrogen needs for the above hydrogasifying step.
 2. The process ofclaim 1 further comprising the steps of:a) recovering thermal energyfrom synthesis gas stream exiting the steam pyrolysis reactor for use inthe present process.
 3. The process of claim 1 wherein thehydrogasifying step includes the introduction of steam into thehydrogasification reactor.
 4. The process of claim 3 wherein the molarratio of hydrogen to carbon monoxide in the said synthesis gas isgreater than 2 to 1 and as high as 6 to
 1. 5. The process of claim 1wherein the steam pyrolysis reactor catalyst is a nickel based catalyst.6. The process of claim 1 wherein the methanol synthesis reactorcatalyst is a copper based catalyst.
 7. The process of claim 1 whereinsaid hydrogasification reactor is operated at a temperature in the rangeof 700° C. to 900° C. and a pressure range of 10 atmosphere to 100atmosphere.
 8. The process of claim 1 wherein said steam pyrolysisreactor is operated at a temperature in the range of 900° C. to 1200° C.and a pressure range of 10 atmosphere and 100 atmosphere.
 9. The processof claim 1 comprising the further steps of:a) expanding the process gasstream produced by the hydrogasification reactor to decrease itspressure and temperature prior to pyrolyzing said process gas stream;and b) compressing said synthesis gas stream to adjust the temperatureand pressure thereof to that needed by the methanol synthesis reactor.10. The process of claim 9 further comprises the step of purging theinert gases from the process.
 11. The process of claim 10 furthercomprising the step of removing catalyst poisoning impurities from theprocess prior to feeding any reactants to the pyrolysis reactor. .Iadd.12. The process of claim 1 further comprising the step of providingadditional steam and methane to the steam pyrolysis reactor from anexternal source..Iaddend.